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2 Applications of Hypervalent Iodine(III) Compounds as Polymerization Initiators

2 Applications of Hypervalent Iodine(III) Compounds as Polymerization Initiators

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Viktor V. Zhdankin



Hypervalent

Iodine Chemistry

Preparation, Structure and

Synthetic Applications of

Polyvalent Iodine Compounds



Hypervalent Iodine Chemistry



Hypervalent Iodine Chemistry

Preparation, Structure and Synthetic Applications

of Polyvalent Iodine Compounds



Viktor V. Zhdankin

Department of Chemistry and Biochemistry

University of Minnesota Duluth, Minnesota, USA



This edition first published 2014

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Library of Congress Cataloging-in-Publication Data

Zhdankin, Viktor V., 1956–

Hypervalent iodine chemistry : preparation, structure and synthetic applications of polyvalent iodine

compounds / Viktor V. Zhdankin.

pages cm

Includes index.

ISBN 978-1-118-34103-2 (cloth)

1. Iodine compounds. 2. Organoiodine compounds. 3. Hypervalence (Theoretical chemistry) I. Title.

QD181.I1Z43 2014

546 .7342–dc23

2013020439

A catalogue record for this book is available from the British Library.

ISBN: 9781118341032

Typeset in 10/12pt Times by Aptara Inc., New Delhi, India



Contents



Preface



ix



1 Introduction and General Overview of Polyvalent Iodine Compounds

1.1 Introduction

1.2 Classification and Nomenclature of Polyvalent Iodine Compounds

1.3 Hypervalent Bonding

1.4 General Structural Features

1.4.1

Experimental Structural Studies

1.4.2

Computational Studies

1.5 General Principles of Reactivity

1.5.1

Ligand Exchange and Reductive Elimination

1.5.2

Radical Reactions

1.5.3

Single-Electron Transfer (SET) Reactions

References



1

1

3

4

8

9

11

12

13

14

15

15



2 Preparation, Structure and Properties of Polyvalent Iodine Compounds

2.1 Iodine(III) Compounds

2.1.1

Inorganic Iodine(III) Derivatives

2.1.2

Organoiodine(III) Fluorides

2.1.3

Organoiodine(III) Chlorides

2.1.4

Organo-Iodosyl Compounds

2.1.5

Organoiodine(III) Carboxylates

2.1.6

[Hydroxy(Organosulfonyloxy)Iodo]Arenes

2.1.7

Organoiodine(III) Derivatives of Strong Acids

2.1.8

Iodine(III) Heterocycles

2.1.9

Iodonium Salts

2.1.10 Iodonium Ylides

2.1.11 Iodine(III) Species with Three Carbon Ligands

2.1.12 Iodine(III) Species with I–N Bonds

2.2 Iodine(V) Compounds

2.2.1

Inorganic Iodine(V) Derivatives

2.2.2

Noncyclic and Pseudocyclic Iodylarenes

2.2.3

Iodine(V) Heterocycles

2.2.4

Organoiodine(V) Fluorides

2.3 Iodine(VII) Compounds

References



21

21

21

23

27

31

35

43

48

50

76

99

107

107

114

114

115

120

126

127

128



vi



Contents



3



Hypervalent Iodine Reagents in Organic Synthesis

3.1 Reactions of Iodine(III) Compounds

3.1.1

Fluorinations

3.1.2

Chlorinations

3.1.3

Brominations

3.1.4

Iodinations

3.1.5

Oxidation of Alcohols

3.1.6

Oxidative Functionalization of Carbonyl Compounds

3.1.7

Oxidative Functionalization of Silyl Enol Ethers

3.1.8

Oxidation of Alkenes and Alkynes

3.1.9

Oxidations at the Benzylic or Allylic Position

3.1.10 Oxidative Functionalization of Aromatic Compounds

3.1.11 Oxidative Dearomatization of Phenols and Related Substrates

3.1.12 Oxidative Coupling of Aromatic Substrates

3.1.13 Oxidative Cationic Cyclizations, Rearrangements and Fragmentations

3.1.14 Oxidations at Nitrogen, Sulfur and other Heteroatoms

3.1.15 Azidations

3.1.16 Aminations

3.1.17 Thiocyanations and Arylselenations

3.1.18 Radical Fragmentations, Rearrangements and Cyclizations

3.1.19 Reactions via Alkyliodine(III) Intermediates

3.1.20 Transition Metal Catalyzed Oxidations

3.1.21 Transition Metal Catalyzed Aziridinations and Amidations

3.1.22 Reactions of Iodonium Salts and C-Substituted Benziodoxoles

3.1.23 Reactions of Iodonium Ylides

3.2 Synthetic Applications of Iodine(V) Compounds

3.2.1

Noncyclic and Pseudocyclic Iodylarenes

3.2.2

2-Iodoxybenzoic Acid (IBX)

3.2.3

Dess–Martin Periodinane (DMP)

3.2.4

Inorganic Iodine(V) Reagents

3.3 Synthetic Applications of Iodine(VII) Compounds

References



145

145

146

152

158

160

164

168

171

173

181

182

183

196

201

216

222

230

232

236

248

250

253

260

278

282

283

288

296

302

303

307



4



Hypervalent Iodine Catalysis

4.1 Catalytic Cycles Based on Iodine(III) Species

4.1.1

Oxidative ␣-Functionalization of Carbonyl Compounds

4.1.2

Oxidative Functionalization of Alkenes and Alkynes

4.1.3

Oxidative Bromination of Aromatic Compounds

4.1.4

Oxidative Amination of Aromatic Compounds

4.1.5

Oxidation of Phenolic Substrates to Quinones and Quinols

4.1.6

Oxidative Spirocyclization of Aromatic Substrates

4.1.7

Carbon–Carbon Bond-Forming Reactions

4.1.8

Hofmann Rearrangement of Carboxamides

4.1.9

Oxidation of Anilines

4.2 Catalytic Cycles Based on Iodine(V) Species

4.3 Tandem Catalytic Systems Involving Hypervalent Iodine and other Co-catalysts

4.4 Catalytic Cycles Involving Iodide Anion or Elemental Iodine as Pre-catalysts

References



337

337

338

342

346

347

349

350

354

355

357

358

364

368

377



Contents



vii



5 Recyclable Hypervalent Iodine Reagents

5.1 Polymer-Supported Iodine(III) Reagents

5.2 Polymer-Supported Iodine(V) Reagents

5.3 Recyclable Nonpolymeric Hypervalent Iodine(III) Reagents

5.3.1 Recyclable Iodine(III) Reagents with Insoluble Reduced Form

5.3.2 Recovery of the Reduced Form of a Hypervalent Iodine Reagent Using

Ion-Exchange Resins

5.3.3 Ionic-Liquid-Supported Recyclable Hypervalent Iodine(III) Reagents

5.3.4 Magnetic Nanoparticle-Supported Recyclable Hypervalent Iodine(III) Reagent

5.3.5 Fluorous Recyclable Hypervalent Iodine(III) Reagents

5.4 Recyclable Nonpolymeric Hypervalent Iodine(V) Reagents

5.5 Recyclable Iodine Catalytic Systems

References



381

381

389

391

393

397

400

401

402

405

406

409



6 Reactions of Hypervalent Iodine Reagents in Green Solvents and under

Solvent-Free Conditions

6.1 Reactions of Hypervalent Iodine Reagents in Water

6.2 Reactions of Hypervalent Iodine Reagents in Recyclable Organic Solvents

6.3 Reactions of Hypervalent Iodine Reagents under Solvent-Free Conditions

References



413

413

418

420

422



7 Practical Applications of Polyvalent Iodine Compounds

7.1 Applications of Inorganic Polyvalent Iodine Derivatives

7.2 Applications of Hypervalent Iodine(III) Compounds as Polymerization Initiators

7.3 Application of Iodonium Salts for Fluoridation in Positron Emission Tomography (PET)

7.4 Biological Activity of Polyvalent Iodine Compounds

References



425

425

426

431

440

443



Index



449



Preface



Iodine is the heaviest non-radioactive element in the Periodic Table that is classified as a nonmetal and it

is the largest, the least electronegative and the most polarizable of the halogens. It formally belongs to the

main group p-block elements; however, the bonding description, structural features and reactivity of iodine

compounds differ from the light main-group elements. The electronic structure of polyvalent iodine is best

explained by the hypervalent model of bonding and, therefore, in modern literature organic compounds of

trivalent and pentavalent iodine are commonly named as hypervalent iodine compounds. The reactivity pattern

of hypervalent iodine in many aspects is similar that of transition metals – the reactions of hypervalent iodine

reagents are commonly discussed in terms of oxidative addition, ligand exchange, reductive elimination and

ligand coupling, which are typical of transition metal chemistry.

Since the beginning of the twenty-first century, the organic chemistry of hypervalent iodine compounds has

experienced an unprecedented, explosive development. Hypervalent iodine reagents are now commonly used

in organic synthesis as efficient multipurpose reagents whose chemical properties are similar to derivatives

of mercury, thallium, lead, osmium, chromium and other metals, but without the toxicity and environmental

problems of these heavy metal congeners. One of the most impressive recent achievements in the field of

iodine chemistry has been the discovery of hypervalent iodine catalysis.

This book is the first comprehensive monograph covering all main aspects of the chemistry of organic and

inorganic polyvalent iodine compounds, including applications in chemical research, medicine and industry.

The introductory chapter (Chapter 1) provides a historical background and describes the general classification

of iodine compounds, nomenclature, hypervalent bonding, general structural features and general principles

of reactivity of polyvalent iodine compounds. Chapter 2 gives a detailed description of the preparative

methods and structural features of all known classes of organic and inorganic derivatives of polyvalent

iodine. Chapter 3, the central chapter of the book, deals with the applications of hypervalent iodine reagents

in organic synthesis. Chapter 4 describes the most recent achievements in hypervalent iodine catalysis.

Chapter 5 deals with recyclable polymer-supported and nonpolymeric hypervalent iodine reagents. Chapter 6

covers the “green” reactions of hypervalent iodine reagents, including solvent-free reactions, reactions in

water and reactions in ionic liquids. The final chapter (Chapter 7) provides an overview of important practical

applications of polyvalent iodine compounds in medicine and in industry.

This book is aimed at all chemists interested in iodine compounds, including academic and industrial

researchers in inorganic, organic, physical, medicinal and biological chemistry. It will be particularly useful

to synthetic organic and inorganic chemists, including graduate and advanced undergraduate students. The

book also covers the green chemistry aspects of hypervalent iodine chemistry, including the use of water

as solvent, reactions under solvent-free conditions, recyclable reagents and solvents and catalytic reactions,

which makes it especially useful for industrial chemists. The last chapter provides a detailed summary of

practical applications of polyvalent iodine compounds, including various industrial applications, biological

activity and applications of iodonium salts in PET (positron emission tomography) diagnostics; this chapter

should be especially useful for medical and pharmaceutical researchers. Overall, the book is aimed at a

broad, multidisciplinary readership and specialists working in different areas of chemistry, pharmaceutical

and medical sciences and industry.



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